Quaternary Ammonium Salt of a Polyalkene-Substituted Amine Compound

ABSTRACT

A quaternary ammonium salt detergent made from the reaction product of the reaction of: (a) polyalkene-substituted amine having at least one tertiary amino group; and (b) a quaternizing agent suitable for converting the tertiary amino group to a quaternary nitrogen and the use of such quaternary ammonium salt detergents in a fuel composition to reduce intake valve deposits.

BACKGROUND OF THE INVENTION

The composition of the present invention relates to a quaternaryammonium salt detergent and the use of such quaternary ammonium saltdetergents in a fuel composition to reduce intake valve deposits andremove or clean up existing deposits on the intake valves; and the useof the quaternary ammonium salt in media such as inks, coatings,mill-bases, plastics and paints.

It is well known that liquid fuel contains components that can degradeduring engine operation and form deposits. These deposits can lead toincomplete combustion of the fuel resulting in higher emission andpoorer fuel economy. Fuel additives, such as detergents, are well knownadditives in liquid fuels to help with control or minimize depositformation. As the dynamics and mechanics of an engine continual advance,the requirements of the fuel must evolve to keep up with these engineadvancements. For example, today's engines have injector system thathave smaller tolerances and operate at higher pressure to enhance fuelspray to the compression or combustion chamber. Deposit prevention anddeposit reduction in these new engines has become critical to optimaloperation of today's engines. Advancements in fuel additive technology,such as detergents, have enabled the fuel to keep up with these engineadvancements. Therefore, there is a need for detergent capable ofproviding acceptable performance in a liquid fuel to promote optimaloperation of today's engines.

U.S. Pat. No. 5,000,792 discloses polyesteramine detergent obtainable byreacting 2 parts of polyhydroxycarboxylic acids with 1 part ofdialkylenetriamine.

U.S. Pat. No. 4,171,959 discloses a motor fuel composition containingquaternary ammonium salts of a succinimide. The quaternary ammonium salthas a counterion of a halide, a sulphonate or a carboxylate.

U.S. Pat. No. 4,338,206 and U.S. Pat. No. 4,326,973 discloses fuelcompositions containing a quaternary ammonium salt of a succinimide,wherein the ammonium ion is heterocyclic aromatic (pyridinium ion).

U.S. Pat. No. 4,108,858 discloses a fuel or lubricating oil compositioncontaining a C2 to C4 polyolefin with a Mw of 800 to 1400 salted with apyridinium salt.

U.S. Pat. No. 5,254,138 discloses a fuel composition containing areaction product of a polyalkyl succinic anhydride with a polyaminohydroxyalkyl quaternary ammonium salt.

U.S. Pat. No. 4,056,531 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000bonded to triethylenediamine. The quaternary ammonium salt counterion isselected from halides, phosphates, alkylphosphates, dialkylphosphates,borates, alkylborates, nitrites, nitrates, carbonates, bicarbonates,alkanoates, and O,O-dialkyldihtiophosphates.

U.S. Pat. No. 4,253,980 and U.S. Pat. No. 4,306,070 disclose a fuelcomposition containing a quaternary ammonium salt of an ester-lactone.

U.S. Pat. No. 3,778,371 discloses a lubricating oil or fuel containing aquaternary ammonium salt of a hydrocarbon with a Mw of 350 to 3000; andthe remaining groups to the quaternary nitrogen are selected from thegroup of C1 to C20 alkyl, C2 to C8 hydroxyalkyl, C2 to C20 alkenyl orcyclic groups.

The present invention, therefore, promotes optimal engine operation,that is, increased fuel economy, better vehicle drivability, reducedemissions and less engine maintenance by reducing, minimizing andcontrolling deposit formation.

Many formulations such as inks, paints, mill-bases and plasticsmaterials require effective dispersants for uniformly distributing aparticulate solid in an organic medium. The organic medium may vary froma polar to non-polar organic medium. Dispersants containing terminalbasic groups such as poly(lower alkylene)imine chains are well known andare generally prepared by reaction of the polyimine with polyesterchains containing terminal acid groups, the reaction results in amixture of amide and salt forms. However, many of these dispersants havelimited performance towards viscosity and stability properties, whichwhen incorporated into printing inks or paints give the inks and paintswith poor flow characteristics. Therefore, there is a need for adispersant capable of providing acceptable flow characteristics andhaving stability properties.

U.S. Pat. No. 5,721,358 which discloses a process for copperphthalocyanine production using a dispersant derived from a non-saltedsuccinimide dispersant. The succinimide dispersant is derived from analkyleneamine and polyisobutylene succinic anhydride.

US Application 2003/0213410 discloses a polymer-modified pigmentcomprising a polymer with at least one carboxylic group or salt thereofand at least one coupling agent. The polymer includes derivatives ofpolyamines that have been reacted with an acylating agent such as aceticor succinic anhydride.

GB 1,373,660 discloses polyesteramine dispersants obtainable by reactionof polyhydroxycarboxylic acids with diamines especially alkylenediaminesand their salts thereof.

Therefore, it would be advantageous to have a dispersant with acceptableperformance, which when incorporated into inks, coatings, mill-bases,plastics and paints gives the inks, coatings, mill-bases, plastics orpaints acceptable flow characteristics.

SUMMARY OF THE INVENTION

For the purposes of this application, the reaction product disclosedherein may be described as either a detergent or dispersant depending onthe field of use. For example, in the field of fuel and/or lubricantadditives the term detergent may mean an additive that has the abilityto keep engine parts clean, while in the field of inks, coatings,mill-bases, plastics and paints the term dispersant may mean an additivefor uniformly distributing a particulate solid in an organic medium.

The present invention provides a composition comprising a quaternaryammonium salt which comprises the reaction product of:

a. polyalkene-substituted amine having at least one tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a method for fueling an internalcombustion engine, comprising:

A. supplying to said engine:

-   -   i. a fuel which is liquid at room temperature; and    -   ii. quaternary ammonium salt comprising the reaction product of:        -   a. polyalkene-substituted amine having at least one tertiary            amino group; and        -   b. a quaternizing agent suitable for converting the tertiary            amino group to a quaternary nitrogen.

The present invention additionally provides a method of lubricating aninternal combustion engine comprising:

A. supplying to the crankcase of said engine:

-   -   i. an oil of lubricating viscosity; and    -   ii. quaternary ammonium salt comprising the reaction product of:        -   a. polyalkene-substituted amine having at least one tertiary            amino group; and        -   b. a quaternizing agent suitable for converting the tertiary            amino group to a quaternary nitrogen.

The present invention further provides a composition comprising: (i) aparticulate solid; (ii) an organic medium; and (iii) a quaternaryammonium salt which comprises the reaction product of:

a. polyalkene-substituted amine having at least one tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a paint or ink compositioncomprising a particulate solid, an organic liquid, a binder and aquaternary ammonium salt which comprises the reaction product of:

a. polyalkene-substituted amine having at least one tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The present invention further provides a mill-base comprising aparticulate solid, an organic liquid and a quaternary ammonium saltwhich comprises the reaction product of:

a. polyalkene-substituted amine having at least one tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

Field of the Invention

This invention involves a quaternary ammonium salt, a fuel compositionthat includes the quaternary ammonium salt, and a method of operating aninternal combustion engine with the fuel composition. The compositionsand methods of the present invention minimize, reduce and controldeposit formation in the engine, which reduces fuel consumption,promotes drivability, vehicle maintenance, and reduces emissions whichenables optimal engine operation.

Fuel

The composition of the present invention can comprise a fuel which isliquid at room temperature and is useful in fueling an engine. The fuelis normally a liquid at ambient conditions e.g., room temperature (20 to30° C.). The fuel can be a hydrocarbon fuel, a nonhydrocarbon fuel, or amixture thereof. The hydrocarbon fuel can be a petroleum distillate toinclude a gasoline as defined by ASTM specification D4814 or a dieselfuel as defined by ASTM specification D975. In an embodiment of theinvention the fuel is a gasoline, and in other embodiments the fuel is aleaded gasoline, or a nonleaded gasoline. In another embodiment of thisinvention the fuel is a diesel fuel. The hydrocarbon fuel can be ahydrocarbon prepared by a gas to liquid process to include for examplehydrocarbons prepared by a process such as the Fischer-Tropsch process.The nonhydrocarbon fuel can be an oxygen containing composition, oftenreferred to as an oxygenate, to include an alcohol, an ether, a ketone,an ester of a carboxylic acid, a nitroalkane, or a mixture thereof. Thenonhydrocarbon fuel can include, for example, methanol, ethanol, methylt-butyl ether, methyl ethyl ketone, transesterified oils and/or fatsfrom plants and animals such as rapeseed methyl ester and soybean methylester, and nitromethane. In several embodiments of this invention thefuel can have an oxygenate content on a weight basis that is 1 percentby weight, or 10 percent by weight, or 50 percent by weight, or up to 85percent by weight. Mixtures of hydrocarbon and nonhydrocarbon fuels caninclude, for example, gasoline and methanol and/or ethanol, diesel fueland ethanol, and diesel fuel and a transesterified plant oil such asrapeseed methyl ester. In an embodiment of the invention, the liquidfuel can be an emulsion of water in a hydrocarbon fuel, a nonhydrocarbonfuel, or a mixture thereof. In several embodiments of this invention thefuel can have a sulfur content on a weight basis that is 5000 ppm orless, 1000 ppm or less, 300 ppm or less, 200 ppm or less, 30 ppm orless, or 10 ppm or less. In another embodiment, the fuel can have asulfur content on a weight basis of 1 to 100 ppm. In one embodiment, thefuel contains 0 ppm to 1000 ppm, or 0 to 500 ppm, or 0 to 100 ppm, or 0to 50 ppm, or 0 to 25 ppm, or 0 to 10 ppm, or 0 to 5 ppm of alkalimetals, alkaline earth metals, transition metals or mixtures thereof. Inanother embodiment, the fuel contains 1 to 10 ppm by weight of alkalimetals, alkaline earth metals, transition metals or mixtures thereof. Itis well known in the art that a fuel containing alkali metals, alkalineearth metals, transition metals or mixtures thereof have a greatertendency to form deposits and therefore foul or plug injectors. The fuelof the invention can be present in a fuel composition in a major amountthat is generally greater than 50 percent by weight, and in otherembodiments is present at greater than 90 percent by weight, greaterthan 95 percent by weight, greater than 99.5 percent by weight, orgreater than 99.8 percent by weight.

Quaternary Ammonium Salt

The composition of the present invention comprises an quaternaryammonium salt which comprises the reaction product of: (a)polyalkene-substituted amine having at least one tertiary amino group;(b) a quaternizing agent suitable for converting the tertiary aminogroup to a quaternary nitrogen wherein the quaternizing agent isselected from the group consisting of dialkyl sulfates, alkyl halides,hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combinationwith an acid or mixtures thereof.

Examples of quaternary ammonium salt and methods for preparing the sameare described in the following patents, which are hereby incorporated byreference, U.S. Pat. No. 4,253,980, U.S. Pat. No. 3,778,371, U.S. Pat.No. 4,171,959, U.S. Pat. No. 4,326,973, U.S. Pat. No. 4,338,206, andU.S. Pat. No. 5,254,138.

Polyalkene-Substituted Amine

The polyalkene-substituted amines having at least one tertiary aminogroup of the present invention may be derived from an olefin polymer andan amine, such as, ammonia, monoamines, polyamines or mixtures thereof.They may be prepared by a variety of methods such as those describedhereinafter.

One method of preparation of a polyalkene-substituted amine involvesreacting a halogenated olefin polymer with an amine, as disclosed inU.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433;and 3,822,289.

Another method of preparation of a polyalkene-substituted amine involvesreaction of a hydroformylated olefin with a polyamine and hydrogenatingthe reaction product, as disclosed in U.S. Pat. Nos. 5,567,845 and5,496,383.

Another method of preparation of a polyalkene-substituted amine involvesconverting a polyalkene by means of a conventional epoxidation reagentwith or without a catalyst, into the corresponding epoxide andconverting the epoxide into the polyalkene substituted amine by reactionwith ammonia or an amine under the conditions of reductive animation, asdisclosed in U.S. Pat. No. 5,350,429.

Another method for preparing polyalkene-substituted amine involveshydrogenation of a β-aminonitrile, which is made by reacting an aminewith a nitrile, as disclosed in U.S. Pat. No. 5,492,641.

Yet another method for preparing polyalkene-substituted amine involveshydroformylating an polybutene or polyisobutylene with a catalyst, suchas, rhodium or cobalt, in the presence of CO and H2 at elevatedpressures and temperatures, as disclosed in U.S. Pat. No. 4,832,702.

The above methods for the preparation of polyalkene substituted amineare for illustrative purposes only and are not meant to be an exhaustivelist. The polyalkene-substituted amines of the present invention are notlimited in scope to the methods of their preparation disclosedhereinabove.

In one embodiment, the olefin polymers used to make thepolyalkene-substituted amine of the present invention are derived fromolefin polymers. The olefin polymers can include homopolymers andinterpolymers of polymerizable olefin monomers of 2 to about 16 carbonatoms, and in another embodiment from 2 to about 6 carbon atoms, and inyet another embodiment from 2 to about 4 carbon atoms. The interpolymersare those in which two or more olefin monomers are interpolymerizedaccording to well known conventional procedures to form polyalkeneshaving units within their structure derived from each of said two ormore olefin monomers. Thus “interpolymer(s)” as used herein is inclusiveof copolymers, terpolymers, and tetrapolymers. As will be apparent tothose of ordinary skill in the art, the polyalkenes from which thepolyalkene-substituted amines (a) are derived are often conventionallyreferred to as “polyolefin(s)”.

The olefin monomers from which the olefin polymers are derived includepolymerizable olefin monomers characterized by the presence of one ormore ethylenically unsaturated groups (i.e., >C═C<); that is, they aremonoole-finic monomers such as ethylene, propylene, 1-butene, isobutene(2-methyl-1-butene), 1-octene or polyolefinic monomers (usuallydiolefinic monomers), such as, 1,3-butadiene and isoprene.

The olefin monomers are usually polymerizable terminal olefins; that is,olefins characterized by the presence in their structure of the group>C═CH₂. However, polymerizable internal olefin monomers characterized bythe presence within their structure of the group

can also be used to form the polyalkenes.

Specific examples of terminal and internal olefin monomers, which can beused to prepare the polyalkenes according to conventional, well-knownpolymerization techniques include: ethylene; propylene; the butenes(butylenes), including 1-butene, 2-butene and isobutylene; 1-pentene;1-hexene; 1-heptene; 1-octene; 1-nonene; 1-decene; 2-pentene;propylene-tetramer; diisobutylene; isobutylene trimer; 1,2-butadiene;1,3-butadiene; 1,2-pentadiene; 1,3-pentadiene; 1,4-pentadiene; isoprene;1,5-hexadiene; 2-methyl-5-propyl-1-hexene; 3-pentene; 4-octene; and3,3-dimethyl-1-pentene.

In one embodiment, the olefin polymer is obtained by polymerization of aC₄ refinery stream having a butene content of about 35 to about 75weight percent and isobutene content of about 30 to about 60 weightpercent, in the presence of a Lewis acid catalyst such as aluminumtrichloride or boron trifluoride. These polybutenes typically containpredominantly (greater than about 80% of total repeating units)isobutylene repeating units of the configuration

In another embodiment, the polyalkene substituent of thepolyalkene-substituted amine is derived from a polyisobutylene.

In one embodiment, the amines that can be used to make thepolyalkene-substituted amine include ammonia, monoamines, polyamines, ormixtures thereof, including mixtures of different monoamines, mixturesof different polyamines, and mixtures of monomamines and polyamines(which include diamines). The amines include aliphatic, aromatic,heterocyclic and carbocyclic amines.

The monoamines and polyamines are characterized by the presence withintheir structure of at least one H—N< group. Therefore, they have atleast one primary (e.g., H₂N—) or secondary amine (e.g., 1 H—N<) group.The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic.

The monoamines are generally substituted with a hydrocarbyl group having1 to about 50 carbon atoms. These hydrocarbyl groups can be aliphaticand free from acetylenic unsaturation and contain 1 to about 30 carbonatoms. Saturated aliphatic hydrocarbon radicals containing 1 to about 30carbon atoms are particularly preferred.

In one embodiment, the monoamines can be represented by the formulaHNR¹R² wherein R¹ is a hydrocarbyl group of up to about 30 carbon atomsand R² is hydrogen or a hydrocarbyl group of up to about 30 carbonatoms. Examples of suitable monoamines include methylamine, ethylamine,diethylamine, 2-ethylhexylamine, di-(2-ethylhexyl)amine, n-butylamine,di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine,laurylamine, methyllaurylamine, and oleylamine.

Aromatic monoamines include those monoamines wherein a carbon atom ofthe aromatic ring structure is attached directly to the amine nitrogen.The aromatic ring will usually be a mononuclear aromatic ring (i.e., onederived from benzene) but can include fused aromatic rings, especiallythose derived from naphthalene. Examples of aromatic monoamines include:aniline, di(para-methylphenyl)amine, naphthylamine, andN-(n-butyl)aniline. Examples of aliphatic substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines include: para-dodecylaniline, cyclohexyl-substitutednaphthylamine, and thienyl-substituted aniline respectively.

Hydroxy amines are also included in the class of useful monoamines. Suchcompounds are the hydroxyhydrocarbyl-substituted analogs of theaforementioned monoamines. In one embodiment, the hydroxy monoamines canbe represented by the formula HNR³R⁴, wherein R³ is a hydroxysubstitutedalkyl radical of up to about 30 carbon atoms, and in one embodiment upto about 10 carbon atoms, and R⁴ is a hydroxysubstituted alkyl radicalof up to about 30 carbon atoms, hydrogen, or a hydrocarbyl group of upto about 10 carbon atoms. Examples of hydroxy-substituted monoaminesinclude: ethanolamine, di-3-propanolamine, 4-hydroxybutylamine,diethanolamine, and N-methyl-2-hydroxypropylamine.

In another embodiment, the amine of the polyalkene-substituted amine canbe a polyamine. The polyamine may be aliphatic, cycloaliphatic,heterocyclic or aromatic. Examples of the polyamines include: alkylenepolyamines, hydroxy containing polyamines, arylpolyamines, andheterocyclic polyamines.

The alkylene polyamines include those represented by the formula

wherein n ranges from 1 to about 10, and in one embodiment from 2 toabout 7, and in one embodiment from 2 to about 5, and the “Alkylene”group has from 1 to about 10 carbon atoms, and in one embodiment from 2to about 6, and in one embodiment from 2 to about 4 carbon atoms. R⁵ isindependently hydrogen, aliphatic, hydroxy- or amine-substitutedaliphatic group of up to about 30 carbon atoms. Typically R⁵ is H orlower alkyl (an alkyl group of 1 to about 5 carbon atoms), mosttypically, H. Such alkylene polyamines include: methylene polyamine,ethylene polyamines, butylene polyamines, propylene polyamines,pentylene polyamines, hexylene polyamines and heptylene polyamines. Thehigher homologs of such amines and related aminoalkyl-substitutedpiperazines are also included.

Specific alkylene polyamines useful in preparing thepolyalkene-substituted amines of this invention include: ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, propylene diamine, 3-dimethylaminopropylamine, trimethylenediamine, hexamethylene diamine, decamethylene diamine, octamethylenediamine, di(heptamethylene)triamine, tripropylene tetramine,pentaethylene hexamine, di(trimethylene triamine),N-(2-aminoethyl)piperazine, and 1,4-bis(2-aminoethyl)piperazine.

Ethylene polyamines, such as those mentioned above, are especiallyuseful for reasons of cost and effectiveness. Such polyamines aredescribed in detail under the heading “Diamines and Higher Amines” inthe Encyclopedia of Chemical Technology, Second Edition, Kirk andOthemer, Volume 7, pages 27-39, Interscience Publishers, Division ofJohn Wiley and Sons, 1965. Such compounds are prepared most convenientlyby the reaction of an alkylene chloride with ammonia or by reaction ofan ethylene imine with a ring-opening reagent such as ammonia. Thesereactions result in the production of the somewhat complex mixtures ofalkylene polyamines, including cyclic condensation products such aspiperazines.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave as residuewhat is often termed “polyamine bottoms”. In general, alkylenepolyaminebottoms can be characterized as having less than two, usually less than1% (by weight) material boiling below about 200° C. A typical sample ofsuch ethylene polyamine bottoms obtained from the Dow Chemical Companyof Freeport, Tex. designated “E-100” has a specific gravity at 15.6° C.of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40°C. of 121 centistokes. Gas chromatography analysis of such a samplecontains about 0.93% “Light Ends” (most probably DETA), 0.72% TETA,21.74% tetraethylene pentamine and 76.61%) pentaethylenehexamine andhigher (by weight). These alkylenepolyamine bottoms include cycliccondensation products, such as, piperazine and higher analogs ofdiethylenetriamine, triethylenetetriamine and the like.

The hydroxy containing polyamines can include: hydroxyalkyl alkylenepolyamines having one or more hydroxyalkyl substituents on the nitrogenatoms. Such polyamines may be made by reacting the above-describedalkylenepolyamines with one or more of alkylene oxides (e.g., ethyleneoxide, propylene oxide, and butylene oxide). Similar alkyleneoxide-alkanolamine reaction products may also be used such as theproducts made by reacting primary, secondary or tertiary alkanolamineswith ethylene, propylene or higher epoxides in a 1:1 to 1:2 molar ratio.Reactant ratios and temperatures for carrying out such reactions areknown to those skilled in the art.

In one embodiment, hydroxyalkyl-substituted alkylene polyamines can bethose in which the hydroxyalkyl group is a lower hydroxyalkyl group,i.e., having less than eight carbon atoms. Examples of suchhydroxyalkyl-substituted polyamines include: N-(2-hydroxyethyl)ethylenediamine (also known as 2-(2-Aminoethylamino)ethanol),N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropyl-substituted tetraethylene pentamine, andN-(3-hydroxybutyl)tetramethylene diamine.

The arylpolyamines are analogous to the aromatic monoamines mentionedabove except for the presence within their structure of another aminonitrogen. Some examples of arylpolyamines include:N,N′-di-n-butyl-para-phenylene diamine andbis-(para-aminophenyl)methane.

The heterocyclic mono- and polyamines can include: aziridines,azetidines, azolidines, pyridines, pyrroles, indoles, piperidines,imidazoles, piperazines, isoindoles, purines, morpholines,thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N′-diamino-alkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Typical heterocyclic amines are the saturated 5- and 6-memberedheterocyclic amines containing only nitrogen, oxygen and/or sulfur inthe hetero ring, especially the piperidines, piperazines,thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substitutedpiperazines, morpholine, aminoalkyl-substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especiallypreferred. Usually the aminoalkyl substituents are substituted on anitrogen atom forming part of the hetero ring. Specific examples of suchheterocyclic amines include: N-aminopropylmorpholine,N-aminoethylpiperazine, and N,N′-diaminoethylpiperazine. Hydroxyheterocyclic polyamines are also useful, examples include:N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,parahydroxy-aniline, and N-hydroxyethylpiperazine.

Examples of polyalkene-substituted amines can include:poly(propylene)amine, poly(butene)amine,N,N-dimethylpolyisobutyleneamine; N-polybutenemorpholine,N-poly(butene)ethylenediamine, N-poly(propylene)trimethylenediamine,N-poly(butene)diethylenetriamine,N′,N′-poly(butene)tetraethylenepentamine, andN,N-dimethyl-N′poly(propylene)-1,3-propylenediamine.

The number average molecular weight of the polyalkene-substituted aminescan range from about 500 to about 5000, or from about 500 to about 3000,and in one embodiment from about 1000 to about 1500.

Any of the above polyalkene-substituted amines, which are secondary orprimary amines, may be alkylated to tertiary amines using alkylatingagents, also described herein below as quaternizing agents, such as,dialkyl sulfates; alkyl halides; hydrocarbyl substituted carbonates;hydrocarbyl epoxides in combination with an acid and mixtures thereof.When using certain quaternizing agents, such as, alkyl halides ordialkyl sulfates, it may be necessary to provide of a base or basicagent like sodium carbonate or sodium hydroxide to free the amine fromits protonated salt after alkylation to give the free tertiary amine.Primary amines require two equivalents of alkylating agent and twoequivalents of base to get to a tertiary amine. In one embodiment, thealkylation of a primary amine may often be done in four successivesteps, first a treatment with the alkylating agent and then secondtreatment with a base and then repeating both steps. In anotherembodiment, it the alkylation of a primary amine can be done in onestep, for example, using two moles of alkyl halide in the presences ofan excess of heterogeneous base, such as, sodium carbonate. Exhaustivealkylation of a polyamine can be done in a similar manner using anamount of alkylating agent equal to or in excess of the equivalents ofhydrogens on the nitrogens of the amine and an excess of base. In oneembodiment, the polyamine is partially alkylated to a tertiary amineprior to quaternization.

In another embodiment, alkylating primary amines and secondary amines totertiary amines may also be accomplished using epoxides. Unlike with thealkyl halides, when using an epoxide, no treatment with base is requiredto get to the free amine. Typically, when alkylating amines usingepoxides, one would use at least one mole of epoxide for each hydrogenatom on the amine (e.g., a simple primary amine, such as, R—NH2, wouldrequire two moles of epoxide.) In alkylating to the tertiary amine withan epoxide, neither additional acid nor base is required.

Quaternizing Agent

The composition of the present invention contains a quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen wherein the quaternizing agent is selected from the groupconsisting of dialkyl sulfates, alkyl halides, hydrocarbyl substitutedcarbonates; hydrocarbyl epoxides in combination with an acid andmixtures thereof. When the polyalkene-substituted amine contains solelyprimary or secondary amino groups, it is necessary to alkylate at leastone of the primary or secondary amino groups to a tertiary amino groupas described above.

In one embodiment, alkylation of primary amines and secondary amines ormixtures with tertiary amines may be exhaustively or partially alkylatedto a tertiary amine and further alkylated to a quaternary salt all inone step. In this one step, it is necessary to properly account for thehydrogens on the nitrogens and provide base or acid as required (e.g.,alkylation up to the tertiary amine requires removal (neutralization) ofthe hydrogen (proton) from the product of the alkylation). Withalkylating agents, such as, alkyl halides or dialkyl sulfates, theproduct of alkylation of a primary or secondary amine is a protonatedsalt and needs a source of base to free the amine and to proceed to thequaternary salt with these such agents requires alkylation of thetertiary amine, and the product is the quaternary ammonium halide ormonomethyl sulfate. In contrast, epoxides as alkylating agents do boththe alkylation and the neutralization such that the intermediatealkylation product is already the free amine. To proceed to thequaternary salt with epoxides it is necessary to provide an equivalentof an acid to provide a proton for the hydroxy group and a counter anionfor the salt.

In one embodiment, the quaternizing agent can include: halides, such aschloride, iodide or bromide; hydroxides; sulphonates; alkyl sulphates,such as, dimethyl sulfate; sultones; phosphates; C₁₋₁₂ alkylphosphates;di C₁₋₁₂ alkylphosphates; borates; C₁₋₁₂ alkylborates; nitrites;nitrates; carbonates; bicarbonates; alkanoates; O,O-di C₁₋₁₂alkyldithiophosphates; or mixtures thereof.

In one embodiment, the quaternizing agent may be derived from dialkylsulphates such as dimethyl sulfate, N-oxides, sultones such as propaneand butane sultone; alkyl, or arylalkyl halides such as methyl and ethylchloride, bromide or iodide or benzyl chloride, and a hydrocarbyl (oralkyl) substituted carbonates. If the alkyl halide is benzyl chloride,the aromatic ring is optionally further substituted with alkyl oralkenyl groups.

The hydrocarbyl (or alkyl) groups of the hydrocarbyl substitutedcarbonates may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atomsper group. In one embodiment, the hydrocarbyl substituted carbonatescontain two hydrocarbyl groups that may be the same or different.Examples of suitable hydrocarbyl substituted carbonates include dimethylor diethyl carbonate.

In another embodiment, the quaternizing agent can be a hydrocarbylepoxides, as represented by the following formula, in combination withan acid:

wherein R₁, R², R³ and R_(s) can be independently H or a C₁₋₅₀hydrocarbyl group.

Examples of hydrocarbyl epoxides can include: styrene oxide, ethyleneoxide, propylene oxide, butylene oxide, stilbene oxide and C₂₋₅₀epoxide.

Fluidizer

The composition of the present invention can additionally contain afluidizer.

In one embodiment, the fluidizer can be a polyetheramines, which can berepresented by the formula R[OCF₂CH(R¹)]_(n)A, where R is a hydrocarbylgroup, R¹ is selected from the group consisting of hydrogen, hydrocarbylgroups of 1 to 16 carbon atoms, and mixtures thereof, n is a number from2 to about 50, and A is selected from the group consisting of—OCH₂CH₂CH₂NR²R² and —NR³R³, where each R² is independently hydrogen orhydrocarbyl, and each R³ is independently hydrogen, hydrocarbyl or—[R⁴N(R⁵)]_(p)R⁶, where R⁴ is C₂-C₁₀ alkylene, R⁵ and R⁶ areindependently hydrogen or hydrocarbyl, and p is a number from 1-7. Thesepolyetheramines can be prepared by initially condensing an alcohol oralkylphenol with an alkylene oxide, mixture of alkylene oxides or withseveral alkylene oxides in sequential fashion in a 1:2-50 mole ratio ofhydric compound to alkylene oxide to form a polyether intermediate. U.S.Pat. No. 5,094,667 provides reaction conditions for preparing apolyether intermediate, the disclosure of which is incorporated hereinby reference. In one embodiment, the alcohols can be linear or branchedfrom 1 to 30 carbon atoms, in another embodiment 6 to 20 carbon atoms,in yet another embodiment from 10 to 16 carbon atoms. The alkyl group ofthe alkylphenols can be 1 to 30 carbon atoms, in another embodiment 10to 20 carbon atoms. Examples of the alkylene oxides include ethyleneoxide, propylene oxide or butylene oxide. The number of alkylene oxideunits in the polyether intermediate can be 10-35 or 18-27. The polyetherintermediate can be converted to a polyetheramine by animation withammonia, an amine or a polyamine to form a polyetheramine of the typewhere A is —NR³R³. Published Patent Application EP310875 providesreaction conditions for the animation reaction, the disclosure of whichis incorporated herein by reference. Alternately, the polyetherintermediate can also be converted to a polyetheramine of the type whereA is —OCH₂CH₂CH₂NR²R² by reaction with acrylonitrile followed byhydrogenation. U.S. Pat. No. 5,094,667 provides reaction conditions forthe cyanoethylation and subsequent hydrogenation, the disclosure ofwhich is incorporated herein by reference. Polyetheramines where A is—OCH₂CH₂CH₂NH₂ are typically preferred. Commercial examples ofpolyetheramines are the Techron® range from Chevron and the Jeffamine®range from Huntsman.

In another embodiment, the fluidizer can be a polyether, which can berepresented by the formula R⁷O[CH₂CH(R⁸)O]_(q)H, where R⁷ is ahydrocarbyl group, R⁸ is selected from the group consisting of hydrogen,hydrocarbyl groups of 1 to 16 carbon atoms, and mixtures thereof, and qis a number from 2 to about 50. Reaction conditions for preparation aswell as various embodiments of the polyethers are presented above in thepolyetheramine description for the polyether intermediate. A commercialexample of a polyether is the Lyondell ND® series. Other suitablepolyethers are also available from Dow-Chemicals, Huntsman, and ICI.

In yet another embodiment, the fiuidizer can be a hydrocarbyl-terminatedpoly-(oxyalklene)aminocarbamate as described U.S. Pat. No. 5,503,644.

In yet another embodiment, the fiuidizer can be an alkoxylate, whereinthe alkoxylate can comprise: (i) a polyether containing two or moreester terminal groups; (ii) a polyether containing one or more estergroups and one or more terminal ether groups; or (iii) a polyethercontaining one or more ester groups and one or more terminal aminogroups wherein a terminal group is defined as a group located withinfive connecting carbon or oxygen atoms from the end of the polymer.Connecting is defined as the sum of the connecting carbon and oxygenatoms in the polymer or end group.

An alkoxylate can be represented by the formula:

wherein, R¹⁰ is H, TC(O)—, or a C₁₋₃₆ hydrocarbyl group, wherein T is aC₁₋₃₆ fatty acid hydrocarbyl mixture in tallow fatty acid or a fattyacid free of rosin acid; R²⁰ is H, A, WC(O)—, or mixtures thereof,wherein A is selected from the group consisting of —OCH₂CH₂CH₂NR²R² and—NR³R³ where each R² is independently hydrogen or hydrocarbyl, and eachR³ is independently hydrogen, hydrocarbyl or —[R⁴N(R⁵)]_(p)R⁶ where R⁴is C₂-C₁₀ alkylene, R⁵ and R⁶ are independently hydrogen or hydrocarbyl,and p is a number from 1-7, W is a C₁₋₃₆ hydrocarbyl group; R¹ isselected from the group consisting of hydrogen, hydrocarbyl groups of 1to 16 carbon atoms; X is an integer from 1 to 36; Z is an integer 1 to3; Q can be O or N; provided that if Q is N then d can be an integerfrom 0 to 2 and Z is the integer 3-d; if Q is O then d can be an integer0 to 1 and Z is the integer 2-d and if Q is O and R¹ is C₁₋₃₆hydrocarbyl group then R² is WC(O)—.

Examples of the alkoxylate can include: C₁₂₋₁₅ alcohol initiatedpolypropyleneoxide (22-24) ether amine, Bayer ACTACLEAR ND21-A™ (C₁₂₋₁₅alcohol initiated polypropyleneoxide (22-24) ether-ol), tall oil fattyacid initiated polypropyleneoxide (22-24) ester-ol, butanol initiatedpolypropyleneoxide (23-25) ether-tallow fatty acid ester, glyceroldioleate initiated polypropyleneoxide (23-25) ether-ol, propylene glycolinitiated polypropyleneoxide (33-34) ether tallow fatty acid ester,tallow fatty acid initiated polypropyleneoxide (22-24) ester-ol andC₁₂₋₁₅ alcohol initiated polypropyleneoxide (22-24) ether tallow fattyacid ester.

These alkoxylates can be made from the reaction of a fatty acid such astall oil fatty acids (TOFA), that is, the mixture of fatty acidspredominately oleic and linoleic and contains residual rosin acids ortallow acid that is, the mixture of fatty acids predominately stearic,palmitic and oleic with an alcohol terminated polyether such aspolypropylene glycol in the presence of an acidic catalyst, usuallymethane sulfonic acid. These alkoxylates can also be made from thereaction of glycerol dioleate and propylene oxide in the presence ofcatalyst.

Oil of Lubricating Viscosity

The composition of the present invention can contain an oil oflubricating viscosity. The oil of lubricating viscosity includes naturalor synthetic oils of lubricating viscosity, oil derived fromhydrocracking, hydrogenation, hydrofinishing, unrefined, refined andre-refined oils, or mixtures thereof. In one embodiment, the oil oflubricating viscosity is a carrier fluid for the dispersant and/or otherperformance additives.

Natural oils include animal oils, vegetable oils, mineral oils ormixtures thereof. Synthetic oils include a hydrocarbon oil, asilicon-based oil, a liquid ester of phosphorus-containing acid.Synthetic oils may be produced by Fischer-Tropsch reactions andtypically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes.

Oils of lubricating viscosity may also be defined as specified in theAmerican Petroleum Institute (API) Base Oil InterchangeabilityGuidelines. In one embodiment the oil of lubricating viscosity comprisesan API Group I, II, III, IV, V or mixtures thereof, and in anotherembodiment API Group I, II, III or mixtures thereof.

Miscellaneous

The composition optionally comprises one or more additional performanceadditives. The performance additives can include: metal deactivators,detergents, dispersants, viscosity modifiers, friction modifiers,dispersant viscosity modifiers, extreme pressure agents, antiwearagents, antioxidants, corrosion inhibitors, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors, and mixturesthereof.

The total combined amount of the additional performance additivecompounds present on an oil free basis ranges from 0 wt % to 25 wt % or0.01 wt % to 20 wt % of the composition. Although, one or more of theother performance additives may be present, it is common for the otherperformance additives to be present in different amounts relative toeach other.

In one embodiment, the composition can be in a concentrate formingamount. If the present invention may be in the form of a concentrate(which may be combined with additional oil to form, in whole or in part,a finished lubricant and/or liquid fuel), the ratio of the additive ofthe invention and/or other additional performance additives in an oil oflubricating viscosity and/or liquid fuel, to diluent oil is in the rangeof 80:20 to 10:90 by weight.

Antioxidants include molybdenum dithiocarbamates, sulphurised olefins,hindered phenols, diphenylamines; detergents include neutral oroverbased, Newtonian or non-Newtonian, basic salts of alkali, alkalineearth and transition metals with one or more of phenates, sulfurizedphenates, sulfonates, carboxylic acids, phosphorus acids, mono- and/ordi-thiophosphoric acids, saligenins, an alkylsalicylates, salixarates.

Dispersants include N-substituted long chain alkenyl succinimide as wellas posted treated version thereof, post-treated dispersants includethose by reaction with urea, thiourea, dimercaptothiadiazoles, carbondisulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substitutedsuccinic anhydrides, nitriles, epoxides, boron compounds, and phosphoruscompounds.

Antiwear agents include: metal thiophosphates, especially zincdialkyldithiophosphates; phosphoric acid esters or salt thereof;phosphites; and phosphorus-containing carboxylic esters, ethers, andamides.

Anti-scuffing agents include: organic sulfides and polysulfides, suchas, benzyldisulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide,di-tertiary butyl polysulfide, di-tert-butylsulfide, sulfurizedDiels-Alder adducts or alkyl sulfenyl N′N-dialkyl dithiocarbamates.

Extreme Pressure (EP) agents include: chlorinated wax; organic sulfidesand polysulfides, such as, benzyldisulfide, bis-(chlorobenzyl)disulfide,dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurizedalkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurizedDiels-Alder adducts; phosphosulfurized hydrocarbons; and metalthiocarbamates, such as, zinc dioctyldithiocarbamate.

Friction modifiers include: fatty amines; esters, such as, boratedglycerol esters; partial esters of glycerol, such as, glycerolmonooleate; fatty phosphites; fatty acid amides; fatty epoxides; boratedfatty epoxides; alkoxylated fatty amines; borated alkoxylated fattyamines; metal salts of fatty acids; fatty imidazolines; condensationproducts of carboxylic acids and polyalkylene-polyamines; and aminesalts of alkylphosphoric acids.

Viscosity modifiers include: hydrogenated copolymers ofstyrene-butadiene, ethylene-propylene polymers, polyisobutenes,hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers,polymethacrylate acid esters, polyacrylate acid esters, polyalkylstyrenes, alkenyl aryl conjugated diene copolymers, polyolefins,polyalkylmethacrylates and esters of maleic anhydride-styrenecopolymers.

Dispersant viscosity modifiers (often referred to as DVM) include:functionalized polyolefins, for example, ethylene-propylene copolymersthat have been functionalized with the reaction product of maleicanhydride and an amine; a polymethacrylate functionalized with an amine;and styrene-maleic anhydride copolymers reacted with an amine.

Corrosion inhibitors include: octylamine octanoate; condensationproducts of dodecenyl succinic acid or anhydride and a fatty acid, suchas, oleic acid with a polyamine.

Metal deactivators include: derivatives of dimercaptothiodiazole,1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles or2-alkyldithiobenzothiazoles.

Foam inhibitors include copolymers of ethyl acrylate and2-ethylhexylacrylate and optionally vinyl acetate.

Demulsifiers include polyethylene glycols, polyethylene oxides,polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pourpoint depressants including esters of maleic anhydride-styrene,polymethacrylates, polyacrylates or polyacrylamides.

Seal swell agents include Exxon Necton-37™ (FN 1380) and Exxon MineralSeal Oil.

INDUSTRIAL APPLICATION

In one embodiment, the present invention is useful as a liquid fuel foran internal combustion engine. The internal combustion engine includesspark ignition and compression ignition engines; 2-stroke or 4-strokecycles; liquid fuel supplied via direct injection, indirect injection,port injection and carburetor; common rail and unit injector systems;light (e.g. passenger car) and heavy duty (e.g. commercial truck)engines; and engines fuelled with hydrocarbon and non-hydrocarbon fuelsand mixtures thereof. The engines may be part of integrated emissionssystems incorporating such elements as; EGR systems; aftertreatmentincluding three-way catalyst, oxidation catalyst, NOx absorbers andcatalysts, catalyzed and non-catalyzed particulate traps optionallyemploying fuel-borne catalyst; variable valve timing; and injectiontiming and rate shaping.

In another embodiment, the present invention is useful in coatings,inks, millbases, plastics and paints, especially high solids paints;inks, especially offset, gravure and screen inks, radiation curableinks; non-aqueous ceramic processes, especially tape-coating,doctor-blade, extrusion and injection moulding type processes;composites, cosmetics, adhesives and plastics materials. Additionally,the composition of the present invention is an effective dispersant foruniformly distributing a particulate solid in an organic medium.Examples of suitable particulate solids are pigments for solvent inks;pigments, extenders and fillers for paints and plastics materials;disperse dyes; optical brightening agents and textile auxiliaries forsolvent dyebaths, inks and other solvent application systems; solids foroil-based and inverse-emulsion drilling muds; dirt and solid particlesin dry cleaning fluids; particulate ceramic materials; magneticmaterials and magnetic recording media; fibres such as glass, steel,carbon and boron for composite materials; and biocides, agrochemicalsand pharmaceuticals which are applied as dispersions in organic media.

In one embodiment, the invention provides a composition comprising (i) aparticulate solid; (ii) an organic medium; and (iii) a quaternaryammonium salt which comprises the reaction product of:

a. polyalkene-substituted amine having at least one a tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

In one embodiment, the organic medium is an organic liquid or a plasticsmaterial.

In one embodiment, the composition as claimed in claim 1 wherein theorganic liquid comprises at least 0.1% by weight of a polar organicliquid based on the total organic liquid.

In one embodiment, the particulate solid is a pigment.

In one embodiment, the invention provides a paint or ink compositioncomprising a particulate solid, an organic liquid, a binder and aquaternary ammonium salt which comprises the reaction product of:

a. polyalkene-substituted amine having at least one a tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

The binder is a polymeric material capable of binding the composition onvolatilization of the organic liquid. Binders are polymeric materialsincluding natural and synthetic materials. In one embodiment, bindersinclude poly(meth)acrylates, polystyrenics, polyesters, polyurethanes,alkyds, polysaccharides such as cellulose, and natural proteins such ascasein. In one embodiment, the binder can be present in the compositionat more than 100% based on the amount of particulate solid, more than200%, more than 300% or more than 400%.

In one embodiment, the invention provides a mill-base comprising aparticulate solid, an organic liquid and a quaternary ammonium saltwhich comprises the reaction product of:

a. polyalkene-substituted amine having at least one a tertiary aminogroup; and

b. quaternizing agent suitable for converting the tertiary amino groupto a quaternary nitrogen.

In one embodiment, the solid is an organic pigment from any of therecognised classes of pigments described, for example, in the ThirdEdition of the Colour Index (1971) and subsequent revisions of, andsupplements thereto, under the chapter headed “Pigments”. Examples oforganic pigments are those from the azo, disazo, condensed azo,thioindigo, indanthrone, isoindanthrone, anthanthrone, anthraquinone,isodibenzanthrone, triphendioxazine, quinacridone and phthalocyanineseries, especially copper phthalocyanine and its nuclear halogenatedderivatives, and also lakes of acid, basic and mordant dyes. Carbonblack, although strictly inorganic, behaves more like an organic pigmentin its dispersing properties. In one embodiment, the organic pigmentsare phthalocyanines, especially copper phthalocyanines, monoazos,disazos, indanthrones, anthranthrones, quinacridones and carbon blacks.

Inorganic solids include: extenders and fillers, such as, talc, kaolin,silica, barytes and chalk; particulate ceramic materials, such as,alumina, silica, zirconia, titania, silicon nitride, boron nitride,silicon carbide, boron carbide, mixed silicon-aluminum nitrides andmetal titanates; particulate magnetic materials, such as, the magneticoxides of transition metals, especially iron and chromium, e.g.gamma-Fe₂O₃, Fe₃O₄, cobalt-doped iron oxides, calcium oxide, ferrites,especially barium ferrites; and metal particles, especially metalliciron, nickel, cobalt, copper and alloys thereof.

In one embodiment, the organic medium, which can be present with thecomposition of the reaction product of the invention and particulatesolid, is a plastics material. In another embodiment the organic mediumcan be an organic liquid. The organic liquid may be a non-polar or apolar organic liquid. In one embodiment, non-polar organic liquids arecompounds containing aliphatic groups, aromatic groups or mixturesthereof. The non-polar organic liquids include non-halogenated aromatichydrocarbons (e.g. toluene and xylene), halogenated aromatichydrocarbons (e.g. chlorobenzene, dichlorobenzene, chlorotoluene),non-halogenated aliphatic hydrocarbons (e.g. linear and branchedaliphatic hydrocarbons containing six or more carbon atoms both fullyand partially saturated), halogenated aliphatic hydrocarbons (e.g.dichloromethane, carbon tetrachloride, chloroform, trichloroethane) andnatural non-polar organics (e.g. vegetable oil, sunflower oil, linseedoil, terpenes and glycerides). In one embodiment, thermoplastic resinsinclude: polyolefins, polyesters, polyamides, polycarbonates,polyurethanes, polystyrenics, poly(meth)acrylates, celluloses andcellulose derivatives. The compositions may be prepared in a number ofways but melt mixing and dry solid blending are typical methods. Ifdesired, the compositions may contain other ingredients, for example,resins (where these do not already constitute the organic medium),binders, fluidizing agents anti-sedimentation agents, plasticizers,surfactants, anti-foamers, rheology modifiers, leveling agents, glossmodifiers and preservatives.

A dispersion may be prepared by any of the conventional methods knownfor preparing dispersions. Thus, the particulate solid, the organicmedium, and the dispersant may be mixed in any order, the mixture thenbeing subjected to a mechanical treatment to reduce the particles of thesolid to an appropriate size, for example, by ball milling, beadmilling, gravel milling or plastic milling until the dispersion isformed. Alternatively, the solid may be treated to reduce its particlesize independently or in admixture with either the organic medium or thedispersant, the other ingredient or ingredients then being added and themixture being agitated to provide the composition.

The composition of the present invention is particularly suited toliquid dispersions. In one embodiment, such dispersion compositionscomprise:

-   -   (a) from 0.5 to 70 parts of a particulate solid;    -   (b) from 0.5 to 30 parts of a compound of the quaternary        ammonium salt described above; and    -   (c) from 20 to 99 parts of an organic liquid; wherein all parts        are by weight and the amounts (a)+(b)+(c)=100.        and such dispersions are useful as (liquid) inks, paints, and        mill-bases.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form aring); substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thisinvention, do not alter the predominantly hydrocarbon nature of thesubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); heterosubstituents, that is, substituents which, while having a predominantlyhydrocarbon character, in the context of this invention, contain otherthan carbon in a ring or chain otherwise composed of carbon atoms.Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituentsas pyridyl, furyl, thienyl and imidazolyl. In general, no more than two,preferably no more than one, non-hydrocarbon substituent will be presentfor every ten carbon atoms in the hydrocarbyl group; typically, therewill be no non-hydrocarbon substituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

EXAMPLES

The invention will be further illustrated by the following examples,which sets forth particularly advantageous embodiments. While theexamples are provided to illustrate the present invention, they are notintended to limit it.

Example A Preparation of Polyisobutene-dimethylamine (PIB DMA) viaChlorine

An apparatus suitable to handle chlorine and hydrogen chloride gas(glass reactor, glass stirrer, PTFE joints, glass thermowell forthermocouple) is connected to sodium hydroxide scrubbers. The glassvessel is charged with 1000 g (˜1 mole, 1 equiv.) of low vinylidene 1000Mn polyisobutylene (PIB) and is heated to 110-120° C. and 1 mole (70 g,1 equiv) chlorine bubbled into the reactor over 7 hours. The reaction issparged with nitrogen at 110-120° C. overnight to remove HCl.

The resultant PIB chloride is transferred to an autoclave and theautoclave sealed. For every mole (˜1030 g) PIB chloride 1 mole ofgaseous dimethylamine (45 g) is added and the reaction is heated to160-170° C. for 8 hours, or until no further reduction in pressure isseen. The reaction is cooled to room temperature and the pressure isreleased. Enough Solvesso™ 150 solvent is added to make a 70% w/wactives solution and the reaction is stirred until homogenous. Theresultant PIB-DMA solution is transferred to a separating funnel andwashed twice with 2M sodium hydroxide solution, to remove HQ and NaCl.After separation, the product is dried over MgSO4 and is filteredthrough a Celite™ pad.

Example B Preparation of Polyisobutene-dimethylamine (PIB DMA) viaHydroformylation

High vinylidene polyisobutylene (PIB) (500 g, Mn 950, 0.53 moles), 300 gdodecane and 2.8 g cobalt octacarbonyl is heated in a 2.5 litreautoclave at 280 bar 1:1 CO:H2 for 5 hours at 185° C., while stirring.The mixture is cooled to room temperature and the catalyst is removed bywashing with 400 ml 10% aqueous acetic acid. The product is neutralizedby washing, and the dodecane is stripped off to yield the PIB aldehydeand possibly also PIB alcohol.

A reactor equipped with stirrer, condenser and Dean and Stark trap ischarged with 1 mole (˜980 g) of the above hydroformylated PIB plus 0.5moles of 40% aqueous dimethylamine solution (112.5 g) and 500 mlcyclohexane. The reaction is heated to reflux until no more water isremoved, and the cyclohexane is removed by distillation under vacuum. 1kg of the azomethine product from above is reacted with 100 g Raneynickel and 25000 kPa hydrogen in an autoclave at 200° C. for 4 hours,followed by stripping under vacuum, yielding the final PIB-DMA product.

Example 1 Dimethylsulfate Quaternary Ammonium Salt made from theReaction Product of Example A

The reaction product of Example A, (Mn 1045, 70% active, 41 g, 27.5mmol) is stirred at room temperature in a glass vessel and then dimethylsulphate (3.3 g, 26.2 mmol) is added dropwise over one minute to providethe quaternary ammonium salt. The whole mixture is stirred at roomtemperature for 1 hour under a nitrogen blanket and is sampled andtitrated against bromocresol green indicator.

Example 2 Benzyl-Chloride Quaternary Ammonium Salt made from theReaction Product of Example A

The reaction product of Example A, (Mn 1045, 70% active, 41 g, 27.5mmol) is stirred at room temperature in a glass vessel and then benzylchloride (3.32 g, 26.2 mmol) is added drop wise over one minute toprovide the quaternary ammonium salt. The mixture is stirred at roomtemperature for 1 hour under a nitrogen blanket and is sampled andtitrated against bromocresol green indicator.

Example 3 Dimethylsulfate Quaternary Ammonium Salt made from theReaction Product of Example B

The reaction product of Example B (Mn 995, 23.7 g, 23.8 mmol) is stirredin a glass vessel with 10 g Solvesso™ 150 solvent until homogenous anddimethyl sulphate (2.85 g, 22.6 mmol) is added to provide the quaternaryammonium salt and the reaction is heated at 90° C. for 3 hours under anitrogen blanket. At the end of the 3 hours, the mixture is sampled andtitrated against bromocresol green indicator.

Example 4 Benzyl-Chloride Quaternary Ammonium Salt made from theReaction Product of Example B

The reaction product of Example B (Mn 995, 23.7 g, 23.8 mmol) is stirredin a glass vessel with 10 g Solvesso™ 150 solvent until homogenous andbenzyl chloride (2.86 g, 22.6 mmol) is added to provide the quaternaryammonium salt and the reaction is heated at 90° C. for 3 hours under anitrogen blanket. At the end of the 3 hours, the mixture is sampled andtitrated against bromocresol green indicator.

Example 5 Styrene Oxide Quaternary Ammonium Salt made from the ReactionProduct of Example A

The reaction product of Example A (Mn 1045, 522.5 g, 0.5 moles) is mixedin a reaction vessel with styrene oxide (60 g, 0.5 moles) and is heatedup to 80° C. Once the mixture reaches 80° C., acetic acid (30 g, 0.5moles) is added dropwise over 2 hours to provide the quaternary ammoniumsalt. After the addition of the acetic acid, the temperature of themixture is maintained for 2 to 3 hours. The reaction is monitored byFTIR. The mixture is cool to 50° C. and decanted into a storage vessel.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.As used herein, the expression “consisting essentially of” permits theinclusion of substances that do not materially affect the basic andnovel characteristics of the composition under consideration.

1. A composition comprising a quaternary ammonium salt which comprisesthe reaction product of: a. polyalkene-substituted amine having at leastone tertiary amino group; and b. quaternizing agent suitable forconverting the tertiary amino group to a quaternary nitrogen.
 2. Thecomposition of claim 1, wherein the quaternizing agent is selected fromthe group consisting of dialkyl sulfates; alkyl halides; hydrocarbylsubstituted carbonates; hydrocarbyl epoxides in combination with anacid; and mixtures thereof.
 3. The composition of claim 1, wherein thepolyalkene-substituted amine has a number average molecular weight ofabout 500 to about
 3000. 4. The composition of claim 1, wherein thepolyalkene substituent of the polyalkene-substituted amine is derivedfrom a polyisobutylene.
 5. The composition of claim 1, furthercomprising a fuel which is liquid at room temperature.
 6. Thecomposition of claim 1, further comprising a fiuidizer.
 7. Thecomposition of claim 1, further comprising an oil of lubricatingviscosity.
 8. The composition of claim 7, further comprising componentselected from the group consisting of metal deactivators, detergentsother than those of claim 1, dispersants, viscosity modifiers, frictionmodifiers, dispersant viscosity modifiers, extreme pressure agents,antiwear agents, antioxidants, corrosion inhibitors, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents, wax controlpolymers, scale inhibitors, gas-hydrate inhibitors and mixtures thereof.9. The composition of claim 8, wherein the component is an overbasedmetal containing detergent, zinc dialkyldithiophosphates or mixturesthereof.
 10. A method of fueling an internal combustion enginecomprising: A. supplying to said engine: i. a fuel which is liquid atroom temperature; and ii. quaternary ammonium salt comprising thereaction product of: a. polyalkene-substituted amine having at least onetertiary amino group; and b. a quaternizing agent suitable forconverting the tertiary amino group to a quaternary nitrogen.
 11. Themethod of claim 10, wherein the quaternizing agent is selected from thegroup consisting of dialkyl sulfates; alkyl halides; hydrocarbylsubstituted carbonates; hydrocarbyl epoxides in combination with anacid; or mixtures thereof.
 12. A method of lubricating an internalcombustion engine comprising: A. supplying to the crankcase of saidengine: i. an oil of lubricating viscosity; and ii. quaternary ammoniumsalt comprising the reaction product of: a. polyalkene-substituted aminehaving at least one tertiary amino group; and b. a quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen.
 13. The method of claim 12, wherein the quaternizing agent isselected from the group consisting of dialkyl sulfates; alkyl halides;hydrocarbyl substituted carbonates; hydrocarbyl epoxides in combinationwith an acid; and mixtures thereof.
 14. A composition comprising: (i) aparticulate solid; (ii) an organic medium; and (iii) a quaternaryammonium salt which comprises the reaction product of: a.polyalkene-substituted amine having at least one tertiary amino group;and b. quaternizing agent suitable for converting the tertiary aminogroup to a quaternary nitrogen.
 15. The composition of claim 14, whereinthe organic medium is an organic liquid or a plastics material.
 16. Thecomposition of claim 15, wherein the organic liquid comprises at least0.1% by weight of a polar organic liquid based on the total organicliquid.
 17. The composition of claim 14, wherein the particulate solidis a pigment.
 18. A paint or ink composition comprising a particulatesolid, an organic liquid, a binder and a quaternary ammonium salt whichcomprises the reaction product of: a. polyalkene-substituted aminehaving at least one tertiary amino group; and b. quaternizing agentsuitable for converting the tertiary amino group to a quaternarynitrogen.
 19. A mill-base comprising a particulate solid, an organicliquid and a quaternary ammonium salt which comprises the reactionproduct of: a. polyalkene-substituted amine having at least one tertiaryamino group; and b. quaternizing agent suitable for converting thetertiary amino group to a quaternary nitrogen.